Method of dyeing



Patented Feb. 12, 1946 METHOD OF DYEING Karl Heyman, Montclair, N. 1., assignor to Amerlcan Viscose Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application January '7, 1944,

Serial No. 517,432

16 Claims.

This invention relates to improvements in cles comprising materials that are not readily permeable to water. More particularly, the in-- vention relates to improvements in methods vof dyeing yarns and other shaped articles comprising vinyl polymers, such as polymers of vinyl chloride and copolymers of vinyl acetate with vinyl chloride.

This application is a continuation in partof my-applications Serial Nos. 319,018, filed. Februmethods of dyeing yarns and other shaped arti- Diphenyl Naphthalene Phenanthrene a-Naphthol b-Naphthol Thio-b-naphthol ary 15, 1940, and 322,844, filed March 7, 1940,

No. 311,109, filed December 2'7, 1939.

Materials that are not readily permeable to wewhich are in turn continuations in part oiSerial,

' ter can not be satisfactorily dyed by the ordinary dyeing. procedure used in' dyeing cotton, wool,

natural silk and regenerated cellulose, -When ordinary methods of dyeing are attempted the dyeeither does not penetrate the material-and no dyeing is effected or when dyeing is eflected the color is not fast and leaches iou Yarns and other shaped articles, such as those of cellulose acetate, which are not readily permeable to water have been dyed when treated with a liquid swelling agent, such as alcohol, acetone or acetic acid. The swelling agent apparently forms or opens pores in the material into which the dye penetrates. There are certain objections to the use of liquid swelling agents. Generally a large amount of swelling agentis required. Also the swelling agent has a tendency to weaken the yarn or shaped article.

I have discovered that yarns and other shaped articles comprising vinyl polymers, such as poly-=- mers of vinyl chloride and copolymers of vinyl acetate with vinyl chloride, can bdsuccessi'ully dyed with suspension dyestuffs when the dyeing operation is carried out with aqueous suspensions Of the dyestuffs in the presence of certain normally solid water-insoluble organic compounds which have a solubility in the vinyl polymer of 2% or greater under the conditions at which the dyeing is carried out. By thetterm suspension dyestuffs is meant water-insoluble dyestufl's of the type applicable to cellulose" acetate from a dispersion, (insoluble anthraquinone and ,azo dyes) sometimes reierredto as dispersal yes, and the dyestufls referred to hereinafter in the examples by their trade names, are of this type.

The compounds which are referred to as assistants include:

2A-dichloro-a-naphthol 2,4 dibromo-a-naphthol o-Hydroxydiphenyl 2-chloro-6-phen'ylphe- I no] 4-ehloro-6-phenylphenol 2-chloro-4-phenylphenol 2-bromo-4-phenylphenol o-cyclohexylphenol p-Chlorothymol 2,4-dichloroaniline 2,5-dichloroanlline a-Naphthylamlne b-Naphthylamine Phenyl-a-naphthyl= amine Phenyl-h-naphthyl= amine o -Aminodiphcnyl Fluorenone B-hydrcxyquincllne Dibenayl succinate p=Aminodiphenyi NN-diphenyl ethyl carbamatc b-Naphthonitrile p-Chlorobenzaldehyde 2,4-dimethoxyhenzaldehyde p-Dimethylaminohenzaldehyde o-Hydroxyacetophenone Benzophenone 1 p-Hydroxybenscphe none tone

Camphor Benzalacetone Anisalacetone Benzoylacetone Benzalacetophenone l-hydroxy-Z-acetonaphthone p-Methoxybenzophe none , Benzil Diphenyltriketone Dibenzoylmethane Desoxybenzoin Benzhydrol Phenylbenzylcarbinol Dicyclohexyl phthal-.

ate Phenyl benzoate p-Cresyl benzoate p-Methoxydiphenyl Benzyl-a-naphthylether b-Naphthylmethylether p-Methoxybenzophe-- none - Benzoic anhydride 2,4,6 tribromophenyl acetate I o-Diphenyl acetate Glycerol tribenzoate Dibenzyl phthalate m-Cresyl benzoate n B rying out my improvedmethod oi dyeing an aqueous suspension containing a single assistant or several assistants together may be used. 7 r,

shrinking the mass.

solution and a suitable dispersing agent, such as that known in the trade as Igepon T, are added to the aqueous dye bath containing the suspension dystuit- The assistant is thus precipitated in the dye bath in colloidal or very finely divided form. When amino compounds are used as ass stants they may be dissolved in an acid solution and precipitated and dispersed in an alkaline dye bath. Phenols may be dissolved in an alkaline solution and precipitated and dispersed in an acid The following examples are illustrative of the invention:

Example 1.-Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths havinga dye bath ratio of 1:30 and containing 1.5% suspension dyestuif and 5% b- Naphthol based on the weight of the yarn. The temperatures of the dye baths were 60 C. and

. the duration of the dyeing operation one hour.

dye bath. The yarn or shaped article to be dyed is then treated with the dye bath containing the assistant in any conditional manner. This procedure may be followed using various quantities of dyestufi' and assistants with different dye bath ratios and temperatures of the dye baths depending upon the character of the material being dyed and the type of dyeing that is being carried out. A satisfactory procedure is one in which the dye bath ratio is 1:30 and contains 1.5% suspension dyestufl with 5% or less of the solid waterinsoluble assistant based on the weight of the yarn or shaped article to be dyed. A suitable dye bath temperature is about 50 C. and the duration .of the dyeing operation one hour. Other temperatures may also be used provided the temperaturedoes not exceed the shrinkage tempera ture of the resin article being dyed. 1 My invention may also be carried out by li eliminarily applying the assistant from suspension directly to the yarn or shaped article. When the yarn or shaped article is thereafter immersed in the dye bath, the assistant aids the action of the dye bath on the yarn or shape in the same manner as when it has been added to the dye bath.

. Instead of using either of the above methods,

of the yarn. The temperatures of the dye baths- The dyestufl's that were used were Cibacete Oran e 2R Cibacete Scarlet G Acele Violet B Acele Yellow 3G 1% and Acele Violet B 1% as the dyestuff.

Example 2.Yams comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuif and 5% p-Dimethylamino-benzaldehyde based on the weight were 60 C. and the duration of the dyeing operation one hour. The dyestuifs that were used were Celliton Red Violet RR Phenacyl Navy Blue PV' Phenacyl Red R Celutate Brill. Blue B Cibacete Rubine BS Artisil Direct Yellow 3GP Example 3.Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye 5 baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuff and 1.5% Benzo- I may incorporate the assistant directl within 'the vinyl polymers before the yarn or other shaped article is formed. The yarn'or shaped article containing the assistant is treated with the dye bath (to which no solid assistant need be added) in theordinary manner.

, phenone based" on the weight of the yarn. The temperatures of the dye baths were 60. C. and the duration of the dyeing operation one hour.

The dyestuffs that wereused were No satisfactory explanation for the effectivein most cases, of producing a given dyeing effect.

They exert relatively little'if any swelling action uponithe mass being dyed. Instead of being softened and weakened by subjection to the dye bath as in the case of the liquid swelling agents heretofore used, vinyl resin fibers immediately 65 after removal from the dye bath show no appreciable softening and often have a harsh hand. The effectiveness does not appear to depend on melting of the solid assistant during dyeing, the dyeing being assisted to approximately the same extent regardless of whether the temperatureof the dye bath is above or below the melting point of the assistant. It is surprising and unpredictable thata solid material even in colloidally dispersed condition, would assist-penetration of a resin by an insoluble dyestufl. Besides increased emciency as compared to liquid swellingvagents,

the solid dyeing assistant of the present invention are more reliable than liquid swelling agents in that higher temperatures (that is, temperatures more closely approaching the shrinkage temperature of the resin) can be used without danger of deleteriously affecting the resin mass, such as by softening, weakening, distorting. or

Celliton Fast Pink BA Acele Scarlet G Calconese Orange 3RC Cibacete Violet B Celutate Fast Blue GL Artisil Direct Yellow 36 ex. Phenacyl Red R Example 4.Yams comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuff and 5% o-Hydroxydiphenyl based on the weight of the yarn. The temperatures of the dye baths were C. and the duration of the dyeing operation one hour. The dyestufis that were used were Celliton Pink RF Celliton Red BR Celliton Orange 3RN Cibacete Yellow 2RN Celliton Fast Yellow GRA Cibacete'Yeliow 5G Cibacete Brill. Blue BGG Celliton Fast Blue FFRS Celliton Discharge Violet B Cibacete Discharge Violet 5R Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 3GP ex. conc.

Celliton Fast Brown BRA I Example 5.- -Yarns comprising copolymers of vinyl acetate and vinyl chloride were treated -76 with a bath in a ratio of 1:30 containing 5% articles comprising vinyl polymers, comprising o-Hydroxydiphenyl based on the weight of the yarn at a temperature of 60 C. and for a period of one-half hour. The yarns so treated were then dyed by immersing in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestufi based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 3GP ex. conc. Celliton Fast Brown 5RA .While preferred assistants and procedures have been shown it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim: 1. A method of'dyeing yarns and other shaped articles comprising vinyl polymers. comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufi in the presence of o-cyclohexyb phenol.

6. A method of dyeing yarns and other shaped articles comprising vinyl polymers, comprising: the 'step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufl in the presence of o-hydroxydiphenyl.

'7. Amethod of dyeing yarns andother shaped articles comprising vinyl polymers, comprising the step of treating the-yarn or shaped article with an aqueous dye bath containing a suspension dyestuff in the presence of thio-b-naphthe step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestuff, in the presence of a water-insoluble, normally solid organic compound selected from the group consisting of a-naphthol, b-naphthol, thio-b-naphthol, 2.4-dichloro-a-naphthol. 2.4-dibromo-a-naphthol, o-hydroxydiphenyl, 2-

;chloro-fi-phenylphenol, 4-chloro-6-phenylphenol,

o-cyclohexylphenol, p-chlorothymol, 2-ch1oro-4- phenylphenol, and 2-bromo-4-phenylphenol.

, 2. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shapedarticle with an aqueous dye bath containing a suspension dyestuff, in the presence of a water-insoluble, normally solid organic compound selected from the'group consisting of a-naphthol, b-naphthol, thio-b-naphthol, 2.4-dichioro-a-naphthol, 2.4-dibromo-a-naphtol o-hydroxydiphenyl, 2-chloro-o-phenylphenol, 4-

chloro-o-phenylphenol, o-cyclohexylphenol, p- ,chlorothymol, 2-chloro-4-phenylphenol, and 2- bromo-4-phenylphenol. I

3. A method of dyeing yarns and other shaped articles comprising vinyl polymers, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestuff and a water-insoluble, normally solid organic compound selected from the group 'consisting of a-naphthol, b-naphthol, thio-b-' naphthol, 2.4-dichloro-a-naphthol, 2.4-dibromoa naphthol, o hydroxydiphenyl, 2 chloro-ophenylphenol, 4-chloro-o-phenylphenol, o-cyclothol.

8. 'A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate andvinyl chloride, comprising the step of treating the yarn or shaped articles with an aqueous dye bath containing a suspension .dyest'uft in th presence of o-cyclohexylphenol.

9. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufi in the presence of o-hydroxydiphenyl.

10. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufi in the presence of thio-b-naphthol.

11. A method of dyeing yarns and other shaped articles comprising vinyl polymers, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestuff and o-cyclolfeirylphenol dispersed in the dye bath. I

12. A method of dyeing yarns and other shaped articles comprising vinyl polymers, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufi and o-hydroxydiphenyl dispersed in the dye bath.

13. A method 01' dyeing yarns and other shaped articles comprising vinyl polymers, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestuff and thio-b-naphthol dispersed in the dye bath.

14. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate andvinyl chloride, comprising the step of treating the yarn or shaped article'with an aqueous dye bath containing a suspension dyestufl and o-cyclohexylphenol dispersed in the dye bath.

' 15. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestufi and o-hydroxydiphenyl dispersed in the dye bath.

16. A method of dyeing yarns and other shaped articles comprising copolymers of vinyl acetate and vinyl chloride, comprising the step or treating the yarn or shaped article with an aqueous dye bath containing a suspension dyestui! and thio-b-naphthol dispersed in the dye bath. 

